Synthesis of new homoconduritols and homoaminoconduritols

Abstract

(1R*,2R*,4R*,5S*,7S*,8S*)-Methyl 3,6-dioxatetracyclo[6.1.0.0(2,4).0(5,7)]nonane-9-carboxylate (10) and (1S*,2S*,4R*,7R*,8S*)-methyl 3-oxatricyclo[5.1.0.0(2,4)]oct-5-ene-8-carboxylate (11) were synthesized starting from methyl 1,3,5-cycloheptatriene-7-carboxylate. By ring opening of epoxide 11 with CH3OH, isomeric products including (1S*,2S*,4R*,7R*,8S*)-methyl 3-oxatricyclo[5.1.0.]oct-5-ene-8-carboxylate (12) were formed. Homoconduritol F derivatives were obtained from reactions such as epoxidation, cis-hydroxylation and ring opening of 12. Homoaminoconduritol B-1, B-2, and F-2 derivatives were synthesized from the corresponding reactions of 11. Ring opening of ene-epoxide 11 with NaN3 gave azidoalcohol as the sole product. Homodiaminoconduritol A-2,3 and B-2,3 derivatives were also synthesized from ring opening with NaN3 and catalytic hydrogenation reactions of both bis-epoxide 10 and ene-epoxide 11. The formations of the products are discussed. (C) 2016 Published by Elsevier Ltd.